CN102505089B - Biodegradable magnesium-lithium alloy material and preparation method thereof - Google Patents
Biodegradable magnesium-lithium alloy material and preparation method thereof Download PDFInfo
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- CN102505089B CN102505089B CN 201110441336 CN201110441336A CN102505089B CN 102505089 B CN102505089 B CN 102505089B CN 201110441336 CN201110441336 CN 201110441336 CN 201110441336 A CN201110441336 A CN 201110441336A CN 102505089 B CN102505089 B CN 102505089B
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Abstract
The invention discloses a biodegradable magnesium-lithium alloy material and a preparation method of the biodegradable magnesium-lithium alloy material, wherein the biodegradable magnesium-lithium alloy material is composed of 7-14% of lithium, 0.5-5.0% of aluminum, 0.6-3.8% of zinc, 0.01-0.5% of zirconium, 0.1-0.5% of calcium, 0.3-0.7% of strontium and magnesium for the rest; the sum of the weight percentages of the components is 100%. The tensile strength of the material is 170-275 Mpa; the yield strength is 125-255 Mpa; the elongation rate is 15-65%; and the density is 1.31-1.60. The material can be used for processing blood vessel stents and joint prosthesis replacement parts.
Description
Technical field
The present invention relates to a kind of magnesium alloy materials, more particularly say, be meant a kind of biodegradable magnesium lithium alloy material and preparation method thereof that has.
Background technology
Lithium is the lightest metallic element, and its density is 0.53g/cm
3, 1/3rd of magnesium is only arranged, in magnesium alloy, add lithium, its density will be reduced.
1910, when German Masing interacts at research Li, Na, K and Mg, find that interesting structural transformation takes place for Mg and Li, and think that this structure is a superstructure.1934～1936 years, moral, American and Britain three state investigators coincidentally studied the structural transformation of magnesium lithium alloy, have measured binary phase diagram, confirmed that in succession the transformation of hcp-bcc appears in Li content when being increased to 5.7wt%.From nineteen forty-two, U.S. Battelle institute begins to develop on a large scale magnesium lithium alloy, and subsequently, war department and its cooperation have been developed the LA141 alloy and included it in aeronautical material standard A MS4386.Afterwards, utilized LA141 to make the magnesium lithium alloy parts that space shuttle Saturn-V uses.The mid-1960s is to nineteen ninety, and USSR (Union of Soviet Socialist Republics) academy of sciences begins to develop magnesium lithium alloy, has developed MA21, alloys such as MA18, and made intensity and ductility better, organize stable magnesium lithium alloy part.
Nineteen eighty-three Soviet Union scholar has at first realized the superplasticity of MA21 alloy.Initiated the novel process of laser rapid solidification refinement surface layer grain in 1984.
Some universities of Japan, industrial community make full use of the achievement of laying a foundation property of state scholar such as the U.S. and Russia, begin from the end of the eighties, concentrate binary Mg-Li, ternary Mg-Li-Re alloy are studied, in 8Li-1Zn system, obtain maximum superplasticity unit elongation δ=840%, developed 36Li-5Zn, 36Li-5Al isodensity simultaneously and only be the 0.95mg/cm3 alloy also lighter than water.
Other metallic element of many interpolations has the plasticity of Mg-Li alloy of higher-strength but very low, the unit elongation that has even be 0.Therefore, the research of Mg-Li Alloy during Superplastic is more in recent years.1984, the 0.A.Kaibyshev of USSR (Union of Soviet Socialist Republics) studies the superplasticity of MA-21 (Mg-8Li-5.2Al-4.7Cd-0.2Mn-1.38Zn), show that grain fineness number is to have obtained the super behavior of moulding in the material of 15 μ m, its sensitivity of strain rate index value is 0.55, obtains 475% unit elongation under 450 ℃ and 10-2s-1 strain rate.Nineteen ninety, people such as the P.Meternier of the U.S. adopt the foil press welding method to obtain the fine grained texture that grain fineness number is 6～35 μ m in two-phase Mg-9.0Li alloy, and obtain unit elongation up to 460% 150～250 ℃ of temperature ranges.E.M.Taleff etc. made the Mg-9.0Li alloy of grain fineness number less than 6 μ m again afterwards, obtained 450% unit elongation down at 100 ℃.K.Higashi and J.Wolfenstine warm-rolling binary two-phase Mg-8.5Li alloy make it have the maximum unit elongation of non-recrystallization texture material, up to 610%.People such as G.Gonzale-Donel obtain the Mg-9.0Li of 5 μ m and the Mg-9.0Li-5.0B4C material of 3.5 μ m, are respectively 455% and 355% unit elongation 200 ℃ of 10-3s-1 acquisitions.Japan Teng Gu the people such as relates to and as cast condition Mg-8.0Li alloy is obtained 300% unit elongation under 300 ℃.
But the research about the Mg-Li alloy all was confined to α single-phased alloy or alpha+beta two-phase alloys in the past, and the research of seldom relevant β single-phased alloy reports more do not have the data of relative commercial alloy.
At the beginning of 21 century, the whole world is annual because of dead about 1,700 ten thousand people of cardiovascular disorder.Along with aging population is quickened day by day, the cardiovascular disease incidence rate accounts for 1/3 of global death toll also in continuous rising, and along with the quickening of social life rhythm, the trend of the also oriented low age of this illness stratum diffusion.Wherein 80% lowly in being distributed in wait income country, so the control of cardiovascular disorder has become the emphasis that domestic and international medical circle is paid close attention to.Dotter in 1969 utilizes metal ring to make intravascular stent in animal body to keep in the blood vessel blood flow unimpeded first.Sigwart in 1987 etc. have successfully implemented the first routine coronary stent operation.Afterwards, coronary stent is widely accepted as second milestone on coronary atherosclerotic heart disease (coronary heart disease) the stent in the treatment history.At the beginning of 21 century, be that the bracket for eluting medicament of representative then is described as the 3rd milestone with Cypher and TAXUS.Stent has been widely used in the treatment of cardiovascular disorder at present.
The design of angiocarpy bracket and manufacturing are complex processes that relates to a plurality of subjects such as materialogy, mechanics, medical science, biological chemistry.From clinical angle, angiocarpy bracket should have that excellent biological compatibility, suitable mechanics of materials feature, material are easily sterilized, microenvironment is easy to control, must guarantee to allow cell well attach growth after implanting, and has the good cell affinity, human body is had no side effect.
The main method of clinical treatment heart arter angiostenosis is to implant long-term through metal at present.Yet the implantation of through metal still comes with some shortcomings, as forming the restenosis that thrombus causes the implant site blood vessel, long-term local inflammatory response, surrounding tissue is had hormesis, and the mechanical behavior at support implantation place and no support place does not match etc., makes its life-time service become problem.So developing material that a kind of human body degradable absorbs becomes as the coronary stent material and presses for.Developing comparatively sophisticated Biodegradable polymer material obviously becomes the preferred material of this problem of solution, but because its specific tenacity is lower, must increase volume for improving support intensity, and it also may cause acute and long-term Inflammatory response between degradative phase, has therefore limited the use of this this class material.
Have the investigator to propose magnesium and magnesium alloy as the degradable blood vessel bracket material in the recent period, magnesium is one of major element of needed by human, so its corrosion product is biological absorbable, and mechanical property also meets the embedded material requirement.And as support, because the flowability of blood, the hydrogen that produces in the degradation process may not can become the subject matter that the research of development degradable MAGNESIUM METAL support faces.B Heublein implants rat heart blood vessel place with magnesium alloy, studied magnesium alloy in the intravital inflammatory reaction of mouse with generate the influence of hydrogen during implanting because of metallic corrosion, thought that biology can absorb Magnuminium and might become a kind of type material that is used to make angiocarpy bracket.But what pay particular attention to is that magnesium alloy interalloy element kind is numerous, must selection! Must be noted that when this class novel material of research because in-vitro simulated degradable experimentation can not be used for predictor internal corrosion situation, and situation is quite complicated again in the body, so magnesium also must carry out a large amount of biological studies as the application of degradation material.They will possess simultaneously satisfies the requirement of intravascular stent for the mechanics of materials, corrosive nature, has excellent biological compatibility simultaneously, also be that this kind material is except that matrix magnesium, for improving all alloying elements that material property adds also should be major element necessary in the human body, with its corrosion product of intravascular stent of guarantee implanting all is biological absorbable, without any toxic side effect.
Summary of the invention
One of purpose of the present invention provides a kind of biodegradable magnesium lithium alloy material that has.Described have biodegradable magnesium lithium alloy material and be made up of 7%～14% lithium (Li), 0.5%～5.0% aluminium (Al), 0.6%～3.8% zinc (Zn), 0.01%～0.5% zirconium (Zr), 0.1%～0.5% calcium (Ca), 0.3%～0.7% strontium (Sr) and the magnesium (Mg) of surplus, and the weight percent content sum of above-mentioned each composition is 100%.
Two of purpose of the present invention is to propose a kind of preparation to have the method for biodegradable magnesium lithium alloy material, and this method includes the following step:
Step 1: take by weighing each element by the nominal composition proportioning, mix obtaining the melting raw material;
Described nominal composition with biodegradable magnesium lithium alloy material is: the lithium by 7%～14% (Li), 0.5%～5.0% aluminium (Al), 0.6%～3.8% zinc (Zn), 0.01%～0.5% zirconium (Zr), 0.1%～0.5% calcium (Ca), 0.3%～0.7% strontium (Sr) and the magnesium (Mg) of surplus are formed, and the weight percent content sum of above-mentioned each composition is 100%.The mass percent purity of each element is not less than 99.0%.
Step 2: melting system ingot
The melting raw material is put into vacuum arc fumace carry out melting, under inert protective atmosphere, take out after the melting evenly and obtain alloy pig;
Smelting parameter: the vacuum tightness of vacuum arc fumace is≤3 * 10 during melting
-2Pa;
Smelting temperature is 650 ℃～750 ℃;
Smelting time is 2～10min;
Inert protective atmosphere can be that mass percent purity is 99.999% argon gas or contains SF
6Hybrid protection atmosphere;
Step 3: system ingot casting
The induction furnace that the alloy pig that step 2 is prepared is put into quick solidification apparatus melts it fully, by spray to cast, solidify cooling and obtain the column alloy cast ingot;
The induction melting parameter is provided with: the vacuum tightness of vacuum induction furnace is≤1 * 10 during melting
-1Pa, induced current 250～450mA, smelting temperature are 650～750 ℃, smelting time is 5s～30s;
Spray to cast pressure is 0.01～0.1MPa;
Speed of cooling is 10～10
5K/s;
Step 4: ingot casting peeling
After the column alloy cast ingot that step 2 is prepared is removed patina by the lathe cutting, insert and carry out cleaning surfaces in the acidic solution and handle 3～10min, obtain cleaning ingot casting;
Step 5: the one-level homogenizing is handled
To clean ingot casting and under 350 ℃ ± 10 ℃ temperature, carry out homogenizing processing 20～36h, obtain the first homogenizing sample;
Step 6: the secondary homogenizing is handled
The first homogenizing sample is carried out homogenizing handle 40～60h under 430 ℃ ± 10 ℃ temperature, obtain the second homogenizing sample.
The advantage of magnesium lithium alloy material of the present invention is: the magnesium lithium alloy material not only has low density 1.31～1.60, advantages of higher tensile strength is that 170～275Mpa, yield strength are 125～255Mpa, and unit elongation is 15～65%.
The erosion rate of magnesium lithium alloy material of the present invention in simulated body fluid is 0.20～0.55mm/year.Described magnesium lithium alloy material possesses simultaneously and satisfies the requirement of intravascular stent for the mechanics of materials, corrosive nature, has excellent biological compatibility simultaneously, also be that this kind material is except that matrix magnesium, for improving all alloying elements that material property adds also should be major element necessary in the human body, with its corrosion product of intravascular stent of guarantee implanting all is biological absorbable, without any toxic side effect.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, refers in particular to as non-, and all units are the unit of being weight percentage all.
A kind of biodegradable magnesium lithium alloy material that has of the present invention, described have biodegradable magnesium lithium alloy material and be made up of 7%～14% lithium (Li), 0.5%～5.0% aluminium (Al), 0.6%～3.8% zinc (Zn), 0.01%～0.5% zirconium (Zr), 0.1%～0.5% calcium (Ca), 0.3%～0.7% strontium (Sr) and the magnesium (Mg) of surplus, and the weight percent content sum of above-mentioned each composition is 100%.
Prepare a kind of method with biodegradable magnesium lithium alloy material of the present invention, it includes following preparation steps:
Step 1: take by weighing each element by the nominal composition proportioning, mix obtaining the melting raw material;
In the present invention, nominal composition with biodegradable magnesium lithium alloy material is: the lithium by 7%～14% (Li), 0.5%～5.0% aluminium (Al), 0.6%～3.8% zinc (Zn), 0.01%～0.5% zirconium (Zr), 0.1%～0.5% calcium (Ca), 0.3%～0.7% strontium (Sr) and the magnesium (Mg) of surplus are formed, and the weight percent content sum of above-mentioned each composition is 100%.The mass percent purity of each element is not less than 99.0%.
Step 2: melting system ingot
The melting raw material is put into vacuum arc fumace carry out melting, under inert protective atmosphere, take out after the melting evenly and obtain alloy pig;
Smelting parameter: the vacuum tightness of vacuum arc fumace is≤3 * 10 during melting
-2Pa;
Smelting temperature is 650 ℃～750 ℃;
Smelting time is 2～10min;
Inert protective atmosphere can be that mass percent purity is 99.999% argon gas or contains SF
6Hybrid protection atmosphere;
Step 3: system ingot casting
The induction furnace that the alloy pig that step 2 is prepared is put into quick solidification apparatus melts it fully, by spray to cast, solidify cooling and obtain the column alloy cast ingot;
The induction melting parameter is provided with: the vacuum tightness of vacuum induction furnace is≤1 * 10 during melting
-1Pa, induced current 250～450mA, smelting temperature are 650～750 ℃, smelting time is 5s～30s;
Spray to cast pressure is 0.01～0.1MPa;
Speed of cooling is 10～10
5K/s;
Step 4: ingot casting peeling
After the column alloy cast ingot that step 2 is prepared is removed patina by the lathe cutting, insert and carry out cleaning surfaces in the acidic solution and handle 3～10min, obtain cleaning ingot casting; Described acidic solution can be hydrofluoric acid, hydrochloric acid etc.;
Step 5: the one-level homogenizing is handled
To clean ingot casting and under 350 ℃ ± 10 ℃ temperature, carry out homogenizing processing 20～36h, obtain the first homogenizing sample;
Step 6: the secondary homogenizing is handled
The first homogenizing sample is carried out homogenizing handle 40～60h under 430 ℃ ± 10 ℃ temperature, obtain the second homogenizing sample;
Step 7: deformation processing
The second homogenizing sample is carried out deformation processing become goods under 25 ± 5 ℃ condition; Perhaps the second homogenizing sample is carried out deformation processing under 250 ℃ ± 5 ℃ condition and become goods.
In the present invention, the goods that obtain of deformation processing can be that intravascular stent, joint are planted and changed part.
Embodiment 1
Step 1: take by weighing each element by the nominal composition proportioning, mix obtaining the melting raw material;
In the present invention, nominal composition with biodegradable magnesium lithium alloy material is: the lithium by 14% (Li), 4% aluminium (Al), 1% zinc (Zn), 0.5% zirconium (Zr), 0.3% calcium (Ca), 0.5% strontium (Sr) and the magnesium (Mg) of surplus are formed, and the weight percent content sum of above-mentioned each composition is 100%.The mass percent purity of each element is not less than 99.0%.
Step 2: melting system ingot
The melting raw material being put into vacuum arc fumace carry out melting, is that melting is evenly taken out and obtained alloy pig in the back under 99.999% the argon gas atmosphere in mass percent purity;
Smelting parameter: the vacuum tightness of vacuum arc fumace is≤3 * 10 during melting
-2Pa;
Smelting temperature is 680 ℃;
Smelting time is 6min;
Step 3: system ingot casting
The induction furnace that the alloy pig that step 2 is prepared is put into quick solidification apparatus melts it fully, by spray to cast, solidify cooling and obtain the column alloy cast ingot;
The induction melting parameter is provided with: the vacuum tightness of vacuum induction furnace is≤1 * 10 during melting
-1Pa, induced current 250mA, smelting temperature are 650 ℃, smelting time is 5s;
Spray to cast pressure is 0.1MPa;
Speed of cooling is 10
2K/s;
Step 4: ingot casting peeling
After the column alloy cast ingot that step 2 is prepared is removed patina by the lathe cutting, insert and carry out cleaning surfaces in the acidic solution and handle 10min, obtain cleaning ingot casting; Described acidic solution is that mass percent concentration is 5% hydrofluoric acid;
Step 5: the one-level homogenizing is handled
To clean ingot casting and under 350 ℃ ± 10 ℃ temperature, carry out homogenizing processing 20～36h, obtain the first homogenizing sample;
Step 6: the secondary homogenizing is handled
The first homogenizing sample is carried out homogenizing handle 40～60h under 430 ℃ ± 10 ℃ temperature, obtain the second homogenizing sample; The density of the second homogenizing sample is 1.31 after tested.
Step 7: deformation processing
The second homogenizing sample is carried out deformation processing become goods under 25 ± 5 ℃ condition.
In the present invention, manual simulation's body fluid includes the KCl of NaCl, the 0.4g of 8.0g, the CaCl of 0.14g
2, 0.35g NaHCO
3, 1.0g C
6H
12O
6The MgCl of (glucose), 0.1g
26H
2The MgSO of O, 0.06g
4The KH of 7HO, 0.06g
2PO
4, 0.06g Na
2HPO
412H
2The deionized water of O and 1L.Regulate pH=7.5 with HCl and NaOH solution, temperature is controlled at 37 ± 1 ℃.The contriver adopts manual simulation's body fluid of preparation the goods that make to be carried out the test of erosion rate.
The goods that embodiment 1 makes are put into manual simulation's body fluid of preparation, and recording erosion rate is 0.25mm/year.
According to navigation mark regulation, use the mode of three-point bending to test the room temperature strength of the second homogenizing sample that embodiment 1 makes, be 6mm/s pressing down speed, the room temperature tensile strength maximum value of the second homogenizing sample is 217Mpa.
The second homogenizing sample that embodiment 1 is prepared adopts universal material mechanical test machine to carry out compression and tension Mechanics Performance Testing discovery, this second homogenizing sample has the good mechanical performance, its yield strength is 216MPa, and has obvious work hardening characteristic.
The second homogenizing sample that embodiment 1 is prepared adopts KDL-100KN elongation test machine to carry out the unit elongation measurement, and recording unit elongation is 27%.
Embodiment 2
Step 1: take by weighing each element by the nominal composition proportioning, mix obtaining the melting raw material;
In the present invention, nominal composition with biodegradable magnesium lithium alloy material is: the lithium by 7% (Li), 1% aluminium (Al), 3.8% zinc (Zn), 0.3% zirconium (Zr), 0.5% calcium (Ca), 0.3% strontium (Sr) and the magnesium (Mg) of surplus are formed, and the weight percent content sum of above-mentioned each composition is 100%.The mass percent purity of each element is not less than 99.0%.
Step 2: melting system ingot
The melting raw material being put into vacuum arc fumace carry out melting, is that melting is evenly taken out and obtained alloy pig in the back under 99.999% the argon gas inert protective atmosphere in mass percent purity;
Smelting parameter: the vacuum tightness of vacuum arc fumace is≤3 * 10 during melting
-2Pa;
Smelting temperature is 750 ℃;
Smelting time is 2min;
Step 3: system ingot casting
The induction furnace that the alloy pig that step 2 is prepared is put into quick solidification apparatus melts it fully, by spray to cast, solidify cooling and obtain the column alloy cast ingot;
The induction melting parameter is provided with: the vacuum tightness of vacuum induction furnace is≤1 * 10 during melting
-1Pa, induced current 300mA, smelting temperature are 680 ℃, smelting time is 10s;
Spray to cast pressure is 0.05MPa;
Speed of cooling is 10
3K/s;
Step 4: ingot casting peeling
After the column alloy cast ingot that step 2 is prepared is removed patina by the lathe cutting, insert and carry out cleaning surfaces in the acidic solution and handle 10min, obtain cleaning ingot casting; Described acidic solution is that mass percent concentration is 15% hydrochloric acid;
Step 5: the one-level homogenizing is handled
To clean ingot casting and under 350 ℃ ± 10 ℃ temperature, carry out homogenizing processing 24h, obtain the first homogenizing sample;
Step 6: the secondary homogenizing is handled
The first homogenizing sample is carried out homogenizing handle 48h under 430 ℃ ± 10 ℃ temperature, obtain the second homogenizing sample; The density of the second homogenizing sample is 1.47 after tested.
Step 7: deformation processing
The second homogenizing sample is carried out deformation processing become goods under 250 ℃ ± 5 ℃ condition.
In the present invention, manual simulation's body fluid includes the KCl of NaCl, the 0.4g of 8.0g, the CaCl of 0.14g
2, 0.35g NaHCO
3, 1.0g C
6H
12O
6The MgCl of (glucose), 0.1g
26H
2The MgSO of O, 0.06g
4The KH of 7HO, 0.06g
2PO
4, 0.06g Na
2HPO
412H
2The deionized water of O and 1L.Regulate pH=7.5 with HCl and NaOH solution, temperature is controlled at 37 ± 1 ℃.The contriver adopts manual simulation's body fluid of preparation the goods that make to be carried out the test of erosion rate.
The goods that embodiment 2 makes are put into manual simulation's body fluid of preparation, and recording erosion rate is 0.55mm/year.
According to navigation mark regulation, use the mode of three-point bending to test the room temperature strength of the second homogenizing sample that embodiment 2 makes, be 6mm/s pressing down speed, the room temperature tensile strength maximum value of the second homogenizing sample is 275Mpa.
The second homogenizing sample that embodiment 2 is prepared adopts universal material mechanical test machine to carry out compression and tension Mechanics Performance Testing discovery, this second homogenizing sample has the good mechanical performance, its yield strength is 167MPa, and has obvious work hardening characteristic.
The second homogenizing sample that embodiment 2 is prepared adopts KDL-100KN elongation test machine to carry out the unit elongation measurement, and recording unit elongation is 63%.
Embodiment 3
Step 1: take by weighing each element by the nominal composition proportioning, mix obtaining the melting raw material;
In the present invention, nominal composition with biodegradable magnesium lithium alloy material is: the lithium by 10% (Li), 5.0% aluminium (Al), 0.6% zinc (Zn), 0.01% zirconium (Zr), 0.1% calcium (Ca), 0.3% strontium (Sr) and the magnesium (Mg) of surplus are formed, and the weight percent content sum of above-mentioned each composition is 100%.The mass percent purity of each element is not less than 99.0%.
Step 2: melting system ingot
The melting raw material is put into vacuum arc fumace carry out melting, at SF
6Inert protective atmosphere under melting evenly take out and obtain alloy pig in the back;
Smelting parameter: the vacuum tightness of vacuum arc fumace is≤3 * 10 during melting
-2Pa;
Smelting temperature is 700 ℃;
Smelting time is 8min;
Step 3: system ingot casting
The induction furnace that the alloy pig that step 2 is prepared is put into quick solidification apparatus melts it fully, by spray to cast, solidify cooling and obtain the column alloy cast ingot;
The induction melting parameter is provided with: the vacuum tightness of vacuum induction furnace is≤1 * 10 during melting
-1Pa, induced current 450mA, smelting temperature are 700 ℃, smelting time is 10s;
Spray to cast pressure is 0.1MPa;
Speed of cooling is 10
5K/s;
Step 4: ingot casting peeling
After the column alloy cast ingot that step 2 is prepared is removed patina by the lathe cutting, insert and carry out cleaning surfaces in the acidic solution and handle 10min, obtain cleaning ingot casting; Described acidic solution is that mass percent concentration is 5% hydrofluoric acid;
Step 5: the one-level homogenizing is handled
To clean ingot casting and under 350 ℃ ± 10 ℃ temperature, carry out homogenizing processing 36h, obtain the first homogenizing sample;
Step 6: the secondary homogenizing is handled
The first homogenizing sample is carried out homogenizing handle 60h under 430 ℃ ± 10 ℃ temperature, obtain the second homogenizing sample; The density of the second homogenizing sample is 1.59 after tested.
Step 7: deformation processing
The second homogenizing sample is carried out deformation processing become goods under 250 ℃ ± 5 ℃ condition.
In the present invention, manual simulation's body fluid includes the KCl of NaCl, the 0.4g of 8.0g, the CaCl of 0.14g
2, 0.35g NaHCO
3, 1.0g C
6H
12O
6The MgCl of (glucose), 0.1g
26H
2The MgSO of O, 0.06g
4The KH of 7HO, 0.06g
2PO
4, 0.06g Na
2HPO
412H
2The deionized water of O and 1L.Regulate pH=7.5 with HCl and NaOH solution, temperature is controlled at 37 ± 1 ℃.The contriver adopts manual simulation's body fluid of preparation the goods that make to be carried out the test of erosion rate.
The goods that embodiment 3 makes are put into manual simulation's body fluid of preparation, and recording erosion rate is 0.47mm/year.
According to navigation mark regulation, use the mode of three-point bending to test the room temperature strength of the second homogenizing sample that embodiment 3 makes, be 6mm/s pressing down speed, the room temperature tensile strength maximum value of the second homogenizing sample is 153Mpa.
The second homogenizing sample that embodiment 3 is prepared adopts universal material mechanical test machine to carry out compression and tension Mechanics Performance Testing discovery, this second homogenizing sample has the good mechanical performance, its yield strength is 255MPa, and has obvious work hardening characteristic.
The second homogenizing sample that embodiment 3 is prepared adopts KDL-100KN elongation test machine to carry out the unit elongation measurement, and recording unit elongation is 17%.
Claims (7)
1. one kind has biodegradable magnesium lithium alloy preparation methods, it is characterized in that including following preparation steps:
Step 1: take by weighing each element by the nominal composition proportioning, mix obtaining the melting raw material;
Described nominal composition with biodegradable magnesium lithium alloy material is: the lithium by 7%～14%, 0.5%～5.0% aluminium, 0.6%～3.8% zinc, 0.01%～0.5% zirconium, 0.1%～0.5% calcium, 0.3%～0.7% strontium and the magnesium of surplus are formed, and the weight percent content sum of above-mentioned each composition is 100%; The mass percent purity of each element is not less than 99.0%;
Step 2: melting system ingot
The melting raw material is put into vacuum arc fumace carry out melting, under inert protective atmosphere, take out after the melting evenly and obtain alloy pig;
Smelting parameter: the vacuum tightness of vacuum arc fumace is≤3 * 10 during melting
-2Pa;
Smelting temperature is 650 ℃～750 ℃;
Smelting time is 2～10min;
Inert protective atmosphere can be that mass percent purity is 99.999% argon gas or contains SF
6Hybrid protection atmosphere;
Step 3: system ingot casting
The induction furnace that the alloy pig that step 2 is prepared is put into quick solidification apparatus melts it fully, by spray to cast, solidify cooling and obtain the column alloy cast ingot;
The induction melting parameter is provided with: the vacuum tightness of vacuum induction furnace is≤1 * 10 during melting
-1Pa, induced current 250～450mA, smelting temperature are 650～750 ℃, smelting time is 5s～30s;
Spray to cast pressure is 0.01～0.1MPa;
Speed of cooling is 10～10
5K/s;
Step 4: ingot casting peeling
After the column alloy cast ingot that step 2 is prepared is removed patina by the lathe cutting, insert and carry out cleaning surfaces in the acidic solution and handle 3～10min, obtain cleaning ingot casting;
Step 5: the one-level homogenizing is handled
To clean ingot casting and under 350 ℃ ± 10 ℃ temperature, carry out homogenizing processing 20～36h, obtain the first homogenizing sample;
Step 6: the secondary homogenizing is handled
The first homogenizing sample is carried out homogenizing handle 40～60h under 430 ℃ ± 10 ℃ temperature, obtain the second homogenizing sample.
2. preparation according to claim 1 has the method for biodegradable magnesium lithium alloy material, it is characterized in that: the second homogenizing sample is carried out deformation processing become goods under 25 ± 5 ℃ condition; Perhaps the second homogenizing sample is carried out deformation processing under 250 ℃ ± 5 ℃ condition and become goods.
3. according to claim 1 have a biodegradable magnesium lithium alloy preparation methods, it is characterized in that: the goods that deformation processing obtains are that intravascular stent, joint are planted and changed part.
4. according to claim 1 have a biodegradable magnesium lithium alloy preparation methods, and it is characterized in that: the described tensile strength with biodegradable magnesium lithium alloy material that makes is 170～275Mpa.
5. according to claim 1 have a biodegradable magnesium lithium alloy preparation methods, it is characterized in that: make described to have biodegradable magnesium lithium alloy YIELD STRENGTH be 125～255Mpa.
6. according to claim 1 have a biodegradable magnesium lithium alloy preparation methods, and it is characterized in that: the described unit elongation with biodegradable magnesium lithium alloy material that makes is 15～65%.
7. according to claim 1 have a biodegradable magnesium lithium alloy preparation methods, and it is characterized in that: the described density of material with biodegradable magnesium lithium alloy material that makes is 1.31～1.60.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110441336 CN102505089B (en) | 2011-12-26 | 2011-12-26 | Biodegradable magnesium-lithium alloy material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 201110441336 CN102505089B (en) | 2011-12-26 | 2011-12-26 | Biodegradable magnesium-lithium alloy material and preparation method thereof |
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| CN102978495A (en) * | 2012-12-13 | 2013-03-20 | 北京大学 | Mg-Sr-Zn alloy and preparation method thereof |
| CN102978493B (en) * | 2012-12-13 | 2015-04-29 | 北京大学 | Mg-Li magnesium alloy and preparation method thereof |
| CN103334037B (en) * | 2013-07-04 | 2015-09-30 | 哈尔滨工程大学 | Si, Sn composite heat-resisting enhance magnesium alloy and plate rolling method |
| CN103436828B (en) * | 2013-09-04 | 2015-06-03 | 中南大学 | Homogenization heat treatment process of large-size magnesium alloy ingot |
| TWI537395B (en) * | 2014-12-02 | 2016-06-11 | 安立材料科技股份有限公司 | Magnesium alloy |
| CN106419987A (en) * | 2016-11-08 | 2017-02-22 | 中南大学 | Intestinal anastomosis ring |
| CN106834843B (en) * | 2017-02-20 | 2018-05-15 | 鼎镁（昆山）新材料科技有限公司 | A kind of high-strength ultralight two phase structure magnesium lithium alloy plate and preparation method thereof |
| CN108727804A (en) * | 2018-05-29 | 2018-11-02 | 合肥智慧龙图腾知识产权股份有限公司 | A kind of bio-medical material and preparation method thereof that degradation property is good |
| US20220275477A1 (en) * | 2019-08-26 | 2022-09-01 | Ohio State Innovation Foundation | Magnesium alloy based objects and methods of making and use thereof |
| CN110860790B (en) * | 2019-11-19 | 2021-03-05 | 中国航空制造技术研究院 | Magnesium-lithium alloy laser welding method and composite shielding gas adopted by same |
| CN113355570A (en) * | 2021-06-23 | 2021-09-07 | 西安四方超轻材料有限公司 | High-elongation soluble magnesium-lithium alloy material and preparation method thereof |
| CN115652156B (en) * | 2022-11-25 | 2023-07-25 | 北京航空航天大学 | Mg-Gd-Li-Y-Al alloy and preparation method thereof |
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| CN1566386A (en) * | 2003-06-18 | 2005-01-19 | 北京有色金属研究总院 | Mg-Zn-Al based magnesium alloy and its smelting method |
| CN1605650A (en) * | 2004-12-01 | 2005-04-13 | 北京航空航天大学 | Aluminum magnesium containing alloy materials and method for making same |
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| CN1605650A (en) * | 2004-12-01 | 2005-04-13 | 北京航空航天大学 | Aluminum magnesium containing alloy materials and method for making same |
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